WO2014157314A1 - Resin composition and coated electric wire - Google Patents

Resin composition and coated electric wire Download PDF

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Publication number
WO2014157314A1
WO2014157314A1 PCT/JP2014/058484 JP2014058484W WO2014157314A1 WO 2014157314 A1 WO2014157314 A1 WO 2014157314A1 JP 2014058484 W JP2014058484 W JP 2014058484W WO 2014157314 A1 WO2014157314 A1 WO 2014157314A1
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mass
parts
electric wire
resin composition
resistance
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PCT/JP2014/058484
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French (fr)
Japanese (ja)
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宏亮 向後
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矢崎総業株式会社
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Priority to US14/777,886 priority Critical patent/US20160272801A1/en
Priority to CN201480016920.0A priority patent/CN105143339A/en
Priority to EP14775902.1A priority patent/EP2980151A1/en
Publication of WO2014157314A1 publication Critical patent/WO2014157314A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/10—Homopolymers or copolymers of propene
    • C09D123/12—Polypropene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/025—Other inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers

Definitions

  • the present invention relates to a resin composition comprising a polypropylene homopolymer as a base and blended with various olefinic resins and a flame retardant, and is stable when used as a resin composition for wire coating.
  • the present invention relates to a resin composition that can be manufactured and that satisfies low temperature resistance, flame resistance, battery fluid resistance, and abrasion resistance when a coating layer for an automobile electric wire specified in 1S06722 is formed.
  • composition proposed in Patent Document 1 is known as a polyolefin-based resin composition for electric wire insulation in automotive electric wire applications.
  • This resin composition comprises (A) 1 to 30 parts by weight of a maleic acid-modified polypropylene resin and 10 parts by weight of a mixture of a polyolefin resin other than the maleic acid-modified polypropylene resin, and (B) 10 to 80 parts by weight of a halogen flame retardant. Part (C) of a metal hydrate flame retardant 5 to 45 parts by weight.
  • the automotive electric wire coated with this resin composition can satisfy various properties such as battery liquid resistance and flame resistance, low temperature resistance, and wear resistance.
  • various properties such as battery liquid resistance and flame resistance, low temperature resistance, and wear resistance.
  • the amount of magnesium hydroxide added is small, it has been found that the viscosity of the resin is low and it is difficult to produce a stable electric wire.
  • the present invention improves the above-described problems, that is, a flame-retardant resin composition obtained by blending magnesium hydroxide with an olefin resin, enables stable production of a covered electric wire, and IS0 6722. It is an object of the present invention to provide a resin composition that can satisfy the battery liquid resistance, flame resistance, low temperature resistance, flame resistance, and wear resistance of an automobile electric wire specified in 1.
  • the present inventors have used a large amount of acid-oxidized metal oxide as a flame retardant, so that stable production of the covered wire, flame resistance, battery resistance I found that I can satisfy my sex.
  • the resin composition of the present invention has (A) polypropylene homopolymer 40 parts by mass or more and 60 parts by mass or less, and (B) polypropylene-based modified resin 1 mass as described in claim 1. Surface relative to 100 parts by mass of the base resin comprising (C) 10 to 25 parts by mass of the thermoplastic elastomer, and (D) 1 to 15 parts by mass of the low density polyethylene. A treated metal hydroxide is blended in an amount of 100 parts by weight or more and 180 parts by weight or less.
  • the covered electric wire of the present invention is a covered electric wire having a covering layer formed of the resin composition according to claim 1 as described in claim 2.
  • the resin composition of the present invention it becomes possible to produce a stable covered electric wire, and the obtained covered electric wire has battery liquid resistance, flame resistance, low temperature resistance of an automobile electric wire specified by IS0 6722, Satisfies flame resistance and wear resistance.
  • FIG. 1 is a model cross-sectional view of an example of a covered electric wire according to the present invention.
  • the resin composition of the present invention (A) 40 to 60 parts by mass of a polypropylene homopolymer, (B) 1 to 30 parts by mass of a polypropylene-based modified resin, and (C) 10 to 10 parts by mass of a thermoplastic elastomer. 25 parts by mass or less, and (D) 100 parts by mass of the surface-treated metal hydroxide is blended by 100 parts by mass or more and 180 parts by mass or less with respect to 100 parts by mass of the base resin composed of 1 part by mass to 15 parts by mass of low density polyethylene. It is necessary to be made.
  • the polyolefin homopolymer is a polypropylene polymerized without using a monomer other than propylene.
  • the use of such a polypropylene homopolymer increases the elasticity as a material and the effect of increasing the wear resistance. Can be obtained.
  • abrasion resistance will become inadequate, and when too large, low temperature resistance will fall.
  • Such polyolefin homopolymers are available from Sun Allomer, such as PS201A, and from SABIC, such as DS531P.
  • the polypropylene-based modified resin used in the present invention is obtained by graft copolymerization of maleic anhydride with a polypropylene resin.
  • a polypropylene-based modified resin may be produced by any method such as a melting method or a solution method.
  • the acid value of maleic anhydride is preferably in the range of 15 to 55, and more preferably in the range of 30 to 40.
  • the acid value is preferably in the range of 15 to 55, and more preferably in the range of 30 to 40.
  • the acid value is too high, it is assumed that unnecessary maleic acid promotes the deterioration of the material.
  • the acid value is too low, the interfacial adhesion between the metal hydroxide and the resin is lowered and the physical properties such as wear are lowered. There is.
  • a preferable compounding amount is 15 parts by mass or more and 25 parts by mass or less.
  • the polypropylene-based modified resin used in the present invention can be obtained from Sanyo Kasei Co., Ltd., Umex 1001, etc., and from DuPont, Fusabond P613, etc., respectively.
  • thermoplastic elastomer used in the present invention an olefin-based and / or styrene-based thermoplastic elastomer can be used.
  • the olefinic thermoplastic elastomer has an olefinic resin such as polyethylene or polypropylene as a hard segment and an olefinic rubber as a soft segment.
  • a blend type (polymer alloy) in which soft segments (domains) are finely dispersed in a hard segment matrix is representative, but a type in which hard segments and soft segments are copolymerized can also be used.
  • the olefin rubber include ethylene-propylene rubber (EPR or EPM) and ethylene-propylene-diene rubber (EPDM). A plurality of these may be used in combination.
  • styrene thermoplastic elastomer examples include a block copolymer or a random copolymer having an aromatic vinyl polymer block (hard segment) and a conjugated diene polymer block (soft segment).
  • aromatic vinyl compounds include ⁇ -alkyl-substituted styrenes such as styrene, ⁇ -methylstyrene, ⁇ -ethylstyrene, ⁇ -methyl-p-methylstyrene, o-methylstyrene, m-methylstyrene, p- Examples thereof include nuclear alkyl-substituted styrene such as methyl styrene, 2,4-dimethyl styrene, ethyl styrene, 2,4,6-trimethyl styrene, ot-butyl styrene, pt-butyl styrene, and p-cyclohex
  • conjugated diene compound examples include butadiene, isoprene, and methylpentadiene.
  • diene rubbers such as styrene-butadiene rubber (SBR), nitrile rubber (NBR), and butyl rubber (IIR) may be used. It is preferable to consist of one or more of the above materials.
  • thermoplastic elastomer If the amount of the thermoplastic elastomer is too small, the low temperature resistance is insufficient, and if it is too large, the wear resistance is lowered.
  • a preferable blending amount is 15 parts by mass or more and 20 parts by mass or less.
  • thermoplastic elastomer that can be used in the present invention can be obtained from Londelbesell, Adflex Q200, etc., and from Mitsubishi Chemical, Thermorun QT60MB, etc., respectively.
  • the low density polyethylene used in the present invention has a density of not less than 0.910 g / cm 3 and O.D. The one with less than 935 g / cm 3 is used.
  • ethylene is polyethylene which is bonded with branches randomly. By using such a low density polyethylene, the effect of improving the wear resistance can be obtained.
  • Polyethylene in which such ethylene is randomly bonded with branches can be obtained from Nippon Polyethylene, such as Novatec LDZE41K, and Londelbesell, 3010D.
  • the preferable blending amount of the low density polyethylene is 8 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin. If the blending amount is too small, the wear resistance becomes insufficient, and if it is too large, the resulting resin composition is softened, so that the wear resistance is lowered.
  • magnesium hydroxide As a flame retardant comprising a surface-treated metal hydrate used in the present invention, as a base material, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, basic magnesium carbonate, hydrated aluminum silicate, hydrated magnesium silicate, etc. Examples thereof include a compound having a hydroxyl group or crystal water and a combination thereof.
  • magnesium hydroxide is particularly preferable as the base material in view of problems such as a decrease in wear resistance due to the addition and foaming which may be generated during processing.
  • a surface that provides resistance to acids such as depositing inorganic substances on the surface of metal hydrates to make them resistant to acids, or covering the surface with fatty acids, silane coupling agents, polymers, etc.
  • the preferable amount of the metal hydrate flame retardant subjected to the surface treatment is 120 parts by mass or more and 140 parts by mass or less with respect to 100 parts by mass of the polyolefin resin. If the blending amount is too small, the flame retardancy becomes insufficient, and if it is too large, the wear resistance and battery fluid resistance are lowered. If necessary, in addition to the surface-treated metal hydrate flame retardant, a metal hydrate such as magnesium hydroxide that has not been surface-treated may be blended and used as appropriate.
  • EP2A is available from Kamishima Chemical Industry
  • Kisuma 5J is available from Kyowa Chemical Industry.
  • the resin composition of the present invention in addition to the above essential components, flame retardants, flame retardant aids, antioxidants, metal deactivators, etc., anti-aging agents, lubricants, as long as the effects of the present invention are not hindered.
  • Fillers and reinforcing materials, UV absorbers, stabilizers, plasticizers, pigments, dyes, colorants, antistatic agents, foaming agents and the like may be blended.
  • the resin composition of the present invention can be obtained by kneading the above-mentioned raw materials with a mixer, a shaft kneader, a Banbury mixer or the like.
  • a coated electric wire can be obtained by extruding the resin composition thus obtained around various metal core wires using an extruder.
  • the resin composition of this invention and a covered electric wire are not limited to the structure of the said embodiment.
  • FIG. 1 shows a model cross-sectional view of these wires.
  • reference numeral 1 denotes a core wire
  • reference numeral 2 denotes a coating layer formed around the core wire 1.
  • ⁇ Electric wire manufacturability> Using 34 types of resin compositions whose compositions are shown in Tables 2 to 5 and using equipment capable of extrusion molding of wires with a linear speed of 300 m / min or more, 0.13 sq wires defined in ISO 6722 are reduced to 0. A coated electric wire was manufactured by coating with a thickness of 2 mmt at a wire speed of 300 m / min or more. At this time, a die having a hole diameter of 1 to 1.5 mm was used.
  • ⁇ Battery liquid resistance> Conforms to ISO6722. That is, a battery solution (sulfuric acid (H 2 SO 4 ) aqueous solution) having a specific gravity of 1.260 ⁇ 0.005 was sprinkled onto the coated electric wire produced above in such a manner that the drops did not contact each other. Such a coating layer in contact with the sulfuric acid solution is kept in an oven at 90 ° C. for 8 hours, then taken out, sprinkled with a battery solution in the same manner as described above, and then placed in an oven at 90 ° C. for 8 hours. Held for hours. Such an operation as one cycle was repeated for a total of 2 cycles, and then allowed to stand at room temperature (23 ° C. ⁇ 5 ° C.) for 30 minutes.
  • this covered electric wire was wound around a predetermined mandrel, and the surface of the wound covered electric wire was visually observed.
  • a withstand voltage test was conducted at 1 kV for 1 minute. Those that were recognized and those in which conduction occurred were evaluated as “x” because the battery liquid resistance was insufficient.
  • ⁇ Flame retardance> Conforms to ISO6722.
  • the covered electric wire is installed in the draft so as to be at an angle of 45 ° C. with respect to the vertical, a Bunsen burner is prepared, and the Bunsen burner is moved so that the installed covered electric wire is positioned in the inner flame portion. Further, the flame contact portion is made to hit a position of 100 mm from the lower end of the installed electric wire. Then, if the cross-sectional area of the conductor is 2.5 mm 2 or less of the wire after 15 seconds, after 30 seconds if the cross-sectional area of the conductor is 2.5 mm 2 or less of the wire, removing the flames from the test sample.
  • ⁇ Low temperature resistance> Conforms to ISO6722.
  • a coated electric wire having a length of 600 mm is used as a sample.
  • a low temperature bath of ⁇ 40 ° C. ⁇ 2 ° C. is used, and a covered wire sample and a mandrel having a diameter five times that of the covered wire are placed in a low temperature bath in advance and sufficiently cooled. Thereafter, the covered electric wire is wound around the mandrel three or more times in the low-temperature tank and then taken out from the cooling tank. After returning to room temperature, the wound part of the covered electric wire was visually observed. At this time, a withstand voltage test of 1 kV for 1 minute was conducted for those for which no conductor exposure was observed. And those in which conduction occurred were evaluated as “x” because the low temperature resistance was insufficient.
  • ⁇ Abrasion resistance> Conforms to ISO6722. Load of 7N, wire diameter 0.45 mm, wire cross-sectional area 0.13 mm 2, and, using a coated electric wire having a coating layer having a thickness of 0.2 mm, measurements were performed in scrape abrasion specification, or 100 times When it was able to withstand this scrape, it was evaluated as “ ⁇ ” because the wear resistance was sufficient, and when the continuity was generated with less than 100 scrapes, it was evaluated as “x” because the wear resistance was insufficient. These evaluation results are also shown in Tables 2 to 5.
  • the resin composition according to the present invention it is possible to produce a stable covered electric wire, and the obtained covered electric wire is a battery liquid resistance and a flame retardant property of an automobile electric wire specified by IS0 6722. It can be seen that it satisfies the properties of heat resistance, low temperature resistance, flame retardancy, and wear resistance.

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Abstract

Provided is a resin composition which enables stable coated electric wire production and by which the obtained coated electric wire satisfies the resistance to battery liquids, flame retardancy, resistance to low temperatures, and abrasion resistance for electric wires for road vehicles stipulated in ISO 6722. The resin composition is obtained by blending 100-180 parts by mass of a surface-treated metal hydroxide with 100 parts by mass of a base resin consisting of (A) 40-60 parts by mass of a polypropylene homopolymer, (B) 1-30 parts by mass of a polypropylene-based modified resin, (C) 10-25 parts by mass of a thermoplastic elastomer and (D) 1-15 parts by mass of low density polyethylene.

Description

樹脂組成物、及び、被覆電線Resin composition and covered electric wire
　本発明は、ポリプロピレン単独重合体をベースとして、各種オレフィン系樹脂と、難燃剤とを配合して構成された樹脂組成物であって、電線被覆用樹脂組成物として用いた場合に安定して電線製造が可能であり、かつ、ｌＳ０６７２２に規定される自動車用電線の被覆層を構成したときに、耐低温性、難燃性、耐バッテリー液性、耐摩耗性を満足する樹脂組成物に関する。 The present invention relates to a resin composition comprising a polypropylene homopolymer as a base and blended with various olefinic resins and a flame retardant, and is stable when used as a resin composition for wire coating. The present invention relates to a resin composition that can be manufactured and that satisfies low temperature resistance, flame resistance, battery fluid resistance, and abrasion resistance when a coating layer for an automobile electric wire specified in 1S06722 is formed.
　自動車用電線用途におけるポリオレフィン系の電線絶縁用樹脂組成物として、特許文献１で提案される組成物が知られている。 The composition proposed in Patent Document 1 is known as a polyolefin-based resin composition for electric wire insulation in automotive electric wire applications.
　この樹脂組成物は、（Ａ）マレイン酸変性ポリプロピレン樹脂１～３０重量部と、該マレイン酸変性ポリプロピレン樹脂以外のポリオレフィン系樹脂との混合物１０重量部、（Ｂ）ハロゲン系難燃剤１０～８０重量部、（Ｃ）金属水和物難燃剤５～４５重量部を含む組成物である。 This resin composition comprises (A) 1 to 30 parts by weight of a maleic acid-modified polypropylene resin and 10 parts by weight of a mixture of a polyolefin resin other than the maleic acid-modified polypropylene resin, and (B) 10 to 80 parts by weight of a halogen flame retardant. Part (C) of a metal hydrate flame retardant 5 to 45 parts by weight.
　この樹脂組成物で被覆されている自動車用電線は、耐バッテリー液性と難燃性、並びに、耐低温性、耐摩耗性などの諸性能を満足することができる。しかし、水酸化マグネシウムの添加量が少ないことから、樹脂の粘度が低く、安定した電線製造が困難であることが判った。 The automotive electric wire coated with this resin composition can satisfy various properties such as battery liquid resistance and flame resistance, low temperature resistance, and wear resistance. However, since the amount of magnesium hydroxide added is small, it has been found that the viscosity of the resin is low and it is difficult to produce a stable electric wire.
特表２００９－４０９４７号公報Special table 2009-40947 gazette
　本発明は、上記の問題点を改善する、すなわち、オレフィン系樹脂に水酸化マグネシウムを配合してなる難燃性樹脂組成物であって、安定した被覆電線の製造が可能となり、かつ、ＩＳ０　６７２２で規定される自動車用電線の耐バッテリー液性、難燃性、耐低温性、難燃性、及び、耐摩耗性を満足することができる樹脂組成物を提供することを目的とする。 The present invention improves the above-described problems, that is, a flame-retardant resin composition obtained by blending magnesium hydroxide with an olefin resin, enables stable production of a covered electric wire, and IS0 6722. It is an object of the present invention to provide a resin composition that can satisfy the battery liquid resistance, flame resistance, low temperature resistance, flame resistance, and wear resistance of an automobile electric wire specified in 1.
　本発明者等は上記目的を達成するために鋭意検討した結果、難燃剤として耐酸性化された金属酸化物を多量に使用することで、被覆電線の安定した製造、難燃性、耐バッテリー液性を満足させることができることを見いだした。 As a result of intensive investigations to achieve the above object, the present inventors have used a large amount of acid-oxidized metal oxide as a flame retardant, so that stable production of the covered wire, flame resistance, battery resistance I found that I can satisfy my sex.
　しかしながら、金属水酸化物を多量に添加することが必要となるので、耐低温性や耐摩耗性が低下してしまうことが判った。 However, since it is necessary to add a large amount of metal hydroxide, it has been found that the low temperature resistance and the wear resistance are lowered.
　そこで、さらに検討を進め、ポリプロピレン（単独重合体）をベースとして、これに、ポリプロピレン系変性樹脂、熱可塑性エラストマー、及び、低密度ポリエチレンを配合すると共に、これらの配合量のバランスを取ることで、上記課題を解決することができた。 Therefore, further studies are conducted, and based on polypropylene (homopolymer), a polypropylene-based modified resin, a thermoplastic elastomer, and low-density polyethylene are blended in this, and by balancing these blending amounts, The above problems could be solved.
　すなわち、本発明の樹脂組成物は上記課題を解決するために、請求項１に記載の通り、（Ａ）ポリプロピレン単独重合体４０質量部以上６０質量部以下、（Ｂ）ポリプロピレン系変性樹脂１質量部以上３０質量部以下、（Ｃ）熱可塑性エラストマー１０質量部以上２５質量部以下、及び、（Ｄ）低密度ポリエチレン１質量部以上１５質量部以下からなるベース樹脂１００質量部に対して、表面処理された金属水酸化物が１００質量部以上１８０質量部以下配合されてなることを特徴とする樹脂組成物である。 That is, in order to solve the above problems, the resin composition of the present invention has (A) polypropylene homopolymer 40 parts by mass or more and 60 parts by mass or less, and (B) polypropylene-based modified resin 1 mass as described in claim 1. Surface relative to 100 parts by mass of the base resin comprising (C) 10 to 25 parts by mass of the thermoplastic elastomer, and (D) 1 to 15 parts by mass of the low density polyethylene. A treated metal hydroxide is blended in an amount of 100 parts by weight or more and 180 parts by weight or less.
　また、本発明の被覆電線は、請求項２に記載の通り、請求項１に記載の樹脂組成物によって形成された被覆層を有することを特徴とする被覆電線ある。 Moreover, the covered electric wire of the present invention is a covered electric wire having a covering layer formed of the resin composition according to claim 1 as described in claim 2.
　本発明の樹脂組成物によれば、安定した被覆電線の製造が可能となり、かつ、得られる被覆電線がＩＳ０　６７２２で規定される自動車用電線の耐バッテリー液性、難燃性、耐低温性、難燃性、及び、耐摩耗性を満足する。 According to the resin composition of the present invention, it becomes possible to produce a stable covered electric wire, and the obtained covered electric wire has battery liquid resistance, flame resistance, low temperature resistance of an automobile electric wire specified by IS0 6722, Satisfies flame resistance and wear resistance.
図１は本発明に係る被覆電線の一例のモデル断面図である。FIG. 1 is a model cross-sectional view of an example of a covered electric wire according to the present invention.
　本発明の樹脂組成物において、（Ａ）ポリプロピレン単独重合体４０質量部以上６０質量部以下、（Ｂ）ポリプロピレン系変性樹脂１質量部以上３０質量部以下、（Ｃ）熱可塑性エラストマー１０質量部以上２５質量部以下、及び、（Ｄ）低密度ポリエチレン１質量部以上１５質量部以下からなるベース樹脂１００質量部に対して、表面処理された金属水酸化物が１００質量部以上１８０質量部以下配合されてなることが必要である。 In the resin composition of the present invention, (A) 40 to 60 parts by mass of a polypropylene homopolymer, (B) 1 to 30 parts by mass of a polypropylene-based modified resin, and (C) 10 to 10 parts by mass of a thermoplastic elastomer. 25 parts by mass or less, and (D) 100 parts by mass of the surface-treated metal hydroxide is blended by 100 parts by mass or more and 180 parts by mass or less with respect to 100 parts by mass of the base resin composed of 1 part by mass to 15 parts by mass of low density polyethylene. It is necessary to be made.
　ポリオレフィン単独重合体とは、プロピレン以外のモノマーを用いないで重合されたポリプロピレンであり、本発明ではこのようなポリプロピレン単独重合体を用いることで、材料としての弾性を高め、耐摩耗性を高める効果を得ることができる。ここで、ポリオレフィン単独重合体の配合量が少なすぎると、耐摩耗性が不十分となり、また、多すぎると耐低温性が低下してしまう。このようなポリオレフィン単独重合体は、サンアロマー社からＰＳ２０１Ａ等が、ＳＡＢＩＣ社からＤＳ５３１Ｐ等が、それぞれ入手できる。 The polyolefin homopolymer is a polypropylene polymerized without using a monomer other than propylene. In the present invention, the use of such a polypropylene homopolymer increases the elasticity as a material and the effect of increasing the wear resistance. Can be obtained. Here, when there are too few compounding quantities of a polyolefin homopolymer, abrasion resistance will become inadequate, and when too large, low temperature resistance will fall. Such polyolefin homopolymers are available from Sun Allomer, such as PS201A, and from SABIC, such as DS531P.
　本発明に用いるポリプロピレン系変性樹脂は無水マレイン酸をポリプロピレン系樹脂にグラフト共重合したものである。このようなポリプロピレン系変性樹脂としては溶融法、あるいは、溶液法、いずれの製法で製造されたものであってもよい。 The polypropylene-based modified resin used in the present invention is obtained by graft copolymerization of maleic anhydride with a polypropylene resin. Such a polypropylene-based modified resin may be produced by any method such as a melting method or a solution method.
　無水マレイン酸の酸価（ＪＩＳ　Ｋ００７０によって測定される）は、１５以上５５以下の範囲であることが好ましく、より好ましくは、３０以上４０以下の範囲である。酸価が高すぎると不要なマレイン酸が材料の劣化を促進することが想定され、低すぎると金属水酸化物と樹脂との界面接着性が低下して摩耗性などの物理特性が低下する場合がある。 The acid value of maleic anhydride (measured according to JIS K0070) is preferably in the range of 15 to 55, and more preferably in the range of 30 to 40. When the acid value is too high, it is assumed that unnecessary maleic acid promotes the deterioration of the material. When the acid value is too low, the interfacial adhesion between the metal hydroxide and the resin is lowered and the physical properties such as wear are lowered. There is.
　ポリプロピレン系変性樹脂の配合量が少なすぎると耐摩耗性が低下し、多すぎると耐低温性が低下する。好ましい配合量は１５質量部以上２５質量部以下である。 If the blending amount of the polypropylene-based modified resin is too small, the wear resistance is lowered, and if it is too much, the low temperature resistance is lowered. A preferable compounding amount is 15 parts by mass or more and 25 parts by mass or less.
　本発明で用いるポリプロピレン系変性樹脂は、三洋化成社からユーメックス１００１等が、デュポン社からフサボンドＰ６１３等が、それぞれ入手できる。 The polypropylene-based modified resin used in the present invention can be obtained from Sanyo Kasei Co., Ltd., Umex 1001, etc., and from DuPont, Fusabond P613, etc., respectively.
　本発明に用いる熱可塑性エラストマーとして、オレフィン系および／またはスチレン系の熱可塑性エラストマーを用いることができる。オレフィン系熱可塑性エラストマーは、ポリエチレン、ポリプロピレン等のオレフィン系樹脂をハードセグメントとし、オレフィン系ゴムをソフトセグメントとするものである。ハードセグメントのマトリックス中にソフトセグメント（ドメイン）を微分散させたブレンドタイプ（ポリマーアロイ）が代表的であるが、ハードセグメントとソフトセグメントとを共重合したタイプも用いることができる。オレフィン系ゴムとしては、例えば、エチレン－プロピレンゴム（ＥＰＲまたはＥＰＭ）、エチレン－プロピレン－ジエンゴム（ＥＰＤＭ）が挙げられる。これらを複数種、組み合わせて使用してもよい。 As the thermoplastic elastomer used in the present invention, an olefin-based and / or styrene-based thermoplastic elastomer can be used. The olefinic thermoplastic elastomer has an olefinic resin such as polyethylene or polypropylene as a hard segment and an olefinic rubber as a soft segment. A blend type (polymer alloy) in which soft segments (domains) are finely dispersed in a hard segment matrix is representative, but a type in which hard segments and soft segments are copolymerized can also be used. Examples of the olefin rubber include ethylene-propylene rubber (EPR or EPM) and ethylene-propylene-diene rubber (EPDM). A plurality of these may be used in combination.
　スチレン系熱可塑性エラストマーとして、芳香族ビニル系重合体ブロック（ハードセグメント）と共役ジエン系重合体ブロック（ソフトセグメント）を有するブロック共重合体もしくはランダム共重合体も挙げられる。芳香族ビニル系化合物の例としては、スチレン、α－メチルスチレン、α－エチルスチレン、α－メチル－ｐ－メチルスチレン等のα－アルキル置換スチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、２，４－ジメチルスチレン、エチルスチレン、２，４，６－トリメチルスチレン、ｏ－ｔ－ブチルスチレン、p－ｔ－ブチルスチレン、ｐ－シクロヘキシルスチレン等の核アルキル置換スチレンなどが挙げられる。 Examples of the styrene thermoplastic elastomer include a block copolymer or a random copolymer having an aromatic vinyl polymer block (hard segment) and a conjugated diene polymer block (soft segment). Examples of aromatic vinyl compounds include α-alkyl-substituted styrenes such as styrene, α-methylstyrene, α-ethylstyrene, α-methyl-p-methylstyrene, o-methylstyrene, m-methylstyrene, p- Examples thereof include nuclear alkyl-substituted styrene such as methyl styrene, 2,4-dimethyl styrene, ethyl styrene, 2,4,6-trimethyl styrene, ot-butyl styrene, pt-butyl styrene, and p-cyclohexyl styrene. .
　共役ジエン系化合物としては、ブタジエン、イソプレン、及びメチルペンタジエン等を挙げることができる。その他ゴム成分として、たとえばスチレン－ブタジェンゴム（ＳＢＲ）、ニトリルゴム（ＮＢＲ）、及び、ブチルゴム（ＩＩＲ）等のジエン系ゴムなどを用いてもよい。上記材料のうち単独または２種以上からなることが好ましい。 Examples of the conjugated diene compound include butadiene, isoprene, and methylpentadiene. As other rubber components, for example, diene rubbers such as styrene-butadiene rubber (SBR), nitrile rubber (NBR), and butyl rubber (IIR) may be used. It is preferable to consist of one or more of the above materials.
　熱可塑性エラストマーの配合量が少なすぎると耐低温性が不十分となり、多すぎると耐摩耗性が低下してしまう。好ましい配合量は１５質量部以上２０質量部以下である。 If the amount of the thermoplastic elastomer is too small, the low temperature resistance is insufficient, and if it is too large, the wear resistance is lowered. A preferable blending amount is 15 parts by mass or more and 20 parts by mass or less.
　本発明で用いることができる熱可塑性エラストマーはＬｙｏｎｄｅｌｌｂｅｓｅｌｌ社からＡｄｆｒｅｘＱ２００等が、三菱化学社からサーモランＱＴ６０ＭＢ等が、それぞれ入手できる。 The thermoplastic elastomer that can be used in the present invention can be obtained from Londelbesell, Adflex Q200, etc., and from Mitsubishi Chemical, Thermorun QT60MB, etc., respectively.
　本発明に用いる低密度ポリエチレンとしては、密度が０，９１０ｇ／ｃｍ３以上Ｏ．９３５ｇ／ｃｍ３未満のものが用いられる。本発明ではエチレンが、ランダムに分岐を持って結合したポリエチレンであることが好ましい。このような低密度ポリエチレンを用いることで耐摩耗性を高める効果を得ることができる。このようなエチレンが、ランダムに分岐を持って結合したポリエチレンは日本ポリエチレン社からノバテックＬＤＺＥ４１Ｋ等が、Ｌｙｏｎｄｅｌｌｂｅｓｅｌｌ社から３０１０Ｄ等が、それぞれ入手できる。 The low density polyethylene used in the present invention has a density of not less than 0.910 g / cm 3 and O.D. The one with less than 935 g / cm 3 is used. In the present invention, it is preferable that ethylene is polyethylene which is bonded with branches randomly. By using such a low density polyethylene, the effect of improving the wear resistance can be obtained. Polyethylene in which such ethylene is randomly bonded with branches can be obtained from Nippon Polyethylene, such as Novatec LDZE41K, and Londelbesell, 3010D.
　低密度ポリエチレンの配合量の好ましい配合量は、樹脂１００質量部に対して８質量部以上１０質量部以下である。配合量が少なすぎると耐摩耗性が不十分となり、多すぎても得られる樹脂組成物が柔軟化するために耐摩耗性が低下してしまう。 The preferable blending amount of the low density polyethylene is 8 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin. If the blending amount is too small, the wear resistance becomes insufficient, and if it is too large, the resulting resin composition is softened, so that the wear resistance is lowered.
　本発明で用いる表面処理された金属水和物からなる難燃剤としては、基材として水酸化マグネシウム、水酸化アルミニウム、水酸化カルシウム、塩基性炭酸マグネシウム、水和珪酸アルミニウム、水和珪酸マグネシウムなどの水酸基あるいは結晶水を有する化合物及びこれらの組合せを挙げることができる。その中でも添加による耐摩耗性の低下や、加工を行う際に発生が懸念される発泡などの問題を考慮すると基材としては水酸化マグネシウムが特に好ましい。 As a flame retardant comprising a surface-treated metal hydrate used in the present invention, as a base material, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, basic magnesium carbonate, hydrated aluminum silicate, hydrated magnesium silicate, etc. Examples thereof include a compound having a hydroxyl group or crystal water and a combination thereof. Among these, magnesium hydroxide is particularly preferable as the base material in view of problems such as a decrease in wear resistance due to the addition and foaming which may be generated during processing.
　表面処理では、酸に対し耐性を持たせるために金属水和物の表面に無機物を析出させる、あるいは、脂肪酸、シランカップリング剤、ポリマー等で表面を覆うなど、酸に対し耐性を付与する表面処理を行う。上記表面処理がなされた金属水和物難燃剤の好ましい配合量は、ポリオレフィン系樹脂１００質量部に対して、１２０質量部以上１４０質量部以下である。配合量が少なすぎると難燃性が不十分となり、多すぎると、耐摩耗性、耐バッテリー液性が低下する。必要に応じ、表面処理がなされた金属水和物難燃剤に加えて、表面処理を行っていない水酸化マグネシウムなどの金属水和物を、ブレンドして使用することも適宜可能である。 In surface treatment, a surface that provides resistance to acids, such as depositing inorganic substances on the surface of metal hydrates to make them resistant to acids, or covering the surface with fatty acids, silane coupling agents, polymers, etc. Process. The preferable amount of the metal hydrate flame retardant subjected to the surface treatment is 120 parts by mass or more and 140 parts by mass or less with respect to 100 parts by mass of the polyolefin resin. If the blending amount is too small, the flame retardancy becomes insufficient, and if it is too large, the wear resistance and battery fluid resistance are lowered. If necessary, in addition to the surface-treated metal hydrate flame retardant, a metal hydrate such as magnesium hydroxide that has not been surface-treated may be blended and used as appropriate.
　本発明で用いることができる表面処理された金属水和物としては、例えば神島化学工業社からＥＰ２Ａ等、協和化学工業社からキスマ５Ｊ等が、それぞれ入手できる。 As the surface-treated metal hydrate that can be used in the present invention, for example, EP2A is available from Kamishima Chemical Industry, and Kisuma 5J is available from Kyowa Chemical Industry.
　本発明の樹脂組成物には、上記必須成分の他、本発明の効果を妨げない範囲で、難燃剤、難燃助剤、酸化防止剤、金属不活性剤、その他、老化防止剤、滑剤、充填剤及び補強材、ＵＶ吸収剤、安定剤、可塑剤、顔料、染料、着色剤、帯電防止剤、発泡剤などが配合されていても良い。 In the resin composition of the present invention, in addition to the above essential components, flame retardants, flame retardant aids, antioxidants, metal deactivators, etc., anti-aging agents, lubricants, as long as the effects of the present invention are not hindered. Fillers and reinforcing materials, UV absorbers, stabilizers, plasticizers, pigments, dyes, colorants, antistatic agents, foaming agents and the like may be blended.
　本発明の樹脂組成物は、上述の原料を、二一ダー、軸型混練機、バンバリーミキサー等で混練して得ることができる。 The resin composition of the present invention can be obtained by kneading the above-mentioned raw materials with a mixer, a shaft kneader, a Banbury mixer or the like.
　さらに、このようにして得た樹脂組成物を押出成形機を用いて各種金属製の芯線の周囲に押出成形することで、被覆電線を得ることができる。 Furthermore, a coated electric wire can be obtained by extruding the resin composition thus obtained around various metal core wires using an extruder.
　以上、本発明について、好ましい実施形態を挙げて説明したが、本発明の樹脂組成物、及び、被覆電線は、上記実施形態の構成に限定されるものではない。 As mentioned above, although this invention was demonstrated and mentioned with preferable embodiment, the resin composition of this invention and a covered electric wire are not limited to the structure of the said embodiment.
　当業者は、従来公知の知見に従い、本発明の樹脂組成物、及び、被覆電線を適宜改変することができる。このような改変によってもなお本発明の樹脂組成物、及び、被覆電線を具備する限り、もちろん、本発明の範疇に含まれるものである。 Those skilled in the art can appropriately modify the resin composition of the present invention and the covered electric wire in accordance with conventionally known knowledge. Of course, such modifications are included in the scope of the present invention as long as the resin composition of the present invention and the covered electric wire are provided.
　表１に示した原料（表中、略号を付した）を用い、表２～表５に示した配合量（質量部）でニーダーを用いて混練して、実施例１～２４、及び、比較例１～１０の計２５種類の樹脂組成物を得た。 Using the raw materials shown in Table 1 (abbreviated in the table), kneading using a kneader at the blending amounts (parts by mass) shown in Tables 2 to 5, Examples 1 to 24 and Comparative Example A total of 25 types of resin compositions of Examples 1 to 10 were obtained.
　これら樹脂組成物を押出成形機を用いて、芯線（素線本数：７本。円形圧縮の計算断面積：約０．１４０７ｍｍ２）の周囲に押出し、外径が０．８８ｍｍの被覆電線（自動車用電線－ＣＨＦＵＳ－０．１３ｓｑ相当）をそれぞれ得た。図1にこれら電線のモデル断面図を示す。図中、符号１は芯線を、符号２は芯線１の周囲に形成された被覆層を、それぞれ示す。 These resin compositions are extruded around a core wire (number of strands: 7; calculated cross-sectional area of circular compression: about 0.1407 mm 2 ) using an extrusion molding machine, and a coated electric wire (automobile) with an outer diameter of 0.88 mm Electric wire—corresponding to CHFUS-0.13 sq). Figure 1 shows a model cross-sectional view of these wires. In the figure, reference numeral 1 denotes a core wire, and reference numeral 2 denotes a coating layer formed around the core wire 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　これら、樹脂組成物及び被覆電線に対して、電線製造性（安定した電線の製造）、耐バッテリー液性、難燃性、耐低温性、及び、耐摩耗性についてそれぞれ評価を行った。 These resin compositions and coated wires were evaluated for wire manufacturability (stable wire production), battery fluid resistance, flame resistance, low temperature resistance, and wear resistance, respectively.
＜電線製造性＞
　表２～表５に組成を示した３４種類の樹脂組成物を用いて、線速３００ｍ／分以上の電線の押出成形が可能な設備を用いて、ＩＳＯ６７２２に規定される０．１３ｓｑ電線を０．２ｍｍｔの肉厚で線速３００ｍ／分以上で被覆し、被覆電線を製造した。このとき、口金として孔径が１～１．５ｍｍのものを用いた。 <Electric wire manufacturability>
Using 34 types of resin compositions whose compositions are shown in Tables 2 to 5 and using equipment capable of extrusion molding of wires with a linear speed of 300 m / min or more, 0.13 sq wires defined in ISO 6722 are reduced to 0. A coated electric wire was manufactured by coating with a thickness of 2 mmt at a wire speed of 300 m / min or more. At this time, a die having a hole diameter of 1 to 1.5 mm was used.
　上記の押出成形時に、安定した電線の製造が可能かどうか評価した。判定基準としては、絶縁層の表面を指で触って平滑であると判断され、かつ、被覆電線をその長さ方向に垂直に切断し、その断面を観察して導線が偏りなく電線の中心に存在すると判断されたときに、安定した電線の製造が可能であり十分であるとして「○」、電線表面が粗いとき、および／あるいは、導体の位置に偏りが発生していた場合に、安定して電線の製造ができないために不十分であるとして「×」として、それぞれ評価した。 It was evaluated whether stable electric wires could be produced during the above extrusion molding. As a criterion for judgment, the surface of the insulating layer is judged to be smooth by touching it with a finger, and the covered electric wire is cut perpendicularly to its length direction, and the cross section is observed so that the conducting wire is not biased to the center of the electric wire. When it is determined that a stable electric wire can be manufactured, it is considered as “○”, and when the surface of the electric wire is rough and / or when the position of the conductor is biased, the electric wire is stable. In this case, it was evaluated as “x” because it was insufficient because the electric wire could not be manufactured.
＜耐バッテリー液性＞
　ＩＳＯ６７２２に準拠する。すなわち、上記で作製した被覆電線に、比重１．２６０±０．００５のバッテリー液（硫酸（Ｈ２ＳＯ４）水溶液）を一滴ずつ、滴同士が互いに接触しないようにして、振りかけた。このような被覆層に硫酸溶液が接触している状態のものを９０℃のオーブン内に８時間保持した後に取り出して、再度、上記同様にバッテリー液を振りかけた後、９０℃のオーブン内に８時間保持した。このような動作を１サイクルとして、計２サイクル繰り返した後、室温（２３℃±５℃）で３０分間放置した。次いで、この被覆電線を所定のマンドレルに巻き付けて、巻き付けられた被覆電線の表面を目視観察した。このとき、導体の露出が認められなかったものについて、１ｋＶ、１分間の耐電圧試験を行い、導通が起こらなかったものを、耐バッテリー液性が十分であるとして「○」、導体の露出が認められたもの、および、導通が起こったものを耐バッテリー液性が不十分であるとして「×」として、それぞれ評価した。 <Battery liquid resistance>
Conforms to ISO6722. That is, a battery solution (sulfuric acid (H 2 SO 4 ) aqueous solution) having a specific gravity of 1.260 ± 0.005 was sprinkled onto the coated electric wire produced above in such a manner that the drops did not contact each other. Such a coating layer in contact with the sulfuric acid solution is kept in an oven at 90 ° C. for 8 hours, then taken out, sprinkled with a battery solution in the same manner as described above, and then placed in an oven at 90 ° C. for 8 hours. Held for hours. Such an operation as one cycle was repeated for a total of 2 cycles, and then allowed to stand at room temperature (23 ° C. ± 5 ° C.) for 30 minutes. Subsequently, this covered electric wire was wound around a predetermined mandrel, and the surface of the wound covered electric wire was visually observed. At this time, with respect to the case where the conductor was not exposed, a withstand voltage test was conducted at 1 kV for 1 minute. Those that were recognized and those in which conduction occurred were evaluated as “x” because the battery liquid resistance was insufficient.
＜難燃性＞
　ＩＳＯ６７２２に準拠する。被覆電線を垂直に対して４５℃の角度となるようにドラフト内に設置し、ブンゼンバーナーを用意し、その内炎部内に、設置された被覆電線が位置するようにブンゼンバーナーを移動させる。また、接炎部は設置した電線の下端から１００ｍｍの位置に当たるようにする。そして、導体の断面積が２．５ｍｍ２以下の電線の場合は１５秒後に、導体の断面積が２．５ｍｍ２以下の電線の場合は３０秒後に、試験試料から炎を外す。このとき、絶縁被膜上の炎が７０秒以内に消え、かつ、試験試料上部の絶縁体が５０ｍｍ以上焼けずに残ったとき、難燃性が十分であるとして「○」、７０秒以上燃え続けるか、あるいは、焼け残った試験試料上部の絶縁体が５０ｍｍ未満の場合、難燃性が不十分であるとして「×」として、それぞれ評価した。 <Flame retardance>
Conforms to ISO6722. The covered electric wire is installed in the draft so as to be at an angle of 45 ° C. with respect to the vertical, a Bunsen burner is prepared, and the Bunsen burner is moved so that the installed covered electric wire is positioned in the inner flame portion. Further, the flame contact portion is made to hit a position of 100 mm from the lower end of the installed electric wire. Then, if the cross-sectional area of the conductor is 2.5 mm 2 or less of the wire after 15 seconds, after 30 seconds if the cross-sectional area of the conductor is 2.5 mm 2 or less of the wire, removing the flames from the test sample. At this time, when the flame on the insulating coating disappears within 70 seconds and the insulator on the top of the test sample remains unburned for 50 mm or more, “○” is assumed to be sufficient for flame retardancy, and it continues to burn for 70 seconds or more. Alternatively, when the unburned insulator on the upper part of the test sample was less than 50 mm, it was evaluated as “x” because the flame retardancy was insufficient.
＜耐低温性＞
　ＩＳＯ６７２２に準拠する。長さ６００ｍｍの被覆電線をサンプルとして使用する。試験に当たり、－４０℃±２℃の低温槽を用い、被覆電線サンプル、および、被覆電線の５倍の径のマンドレルを予め低温槽内に置いて十分に冷却する。その後低温槽内で被覆電線をマンドレルに３周以上巻き付けた後、冷却槽から取り出す。室温に戻った後、被覆電線の、巻き付けられた部分を目視で観察した。このとき、導体の露出が認められなかったものについて、１ｋＶ、１分間の耐電圧試験を行い、導通が起こらなかったものを、耐低温性が十分であるとして「○」、導体の露出が認められたもの、および、導通が起こったものを耐低温性が不十分であるとして「×」として、それぞれ評価した。 <Low temperature resistance>
Conforms to ISO6722. A coated electric wire having a length of 600 mm is used as a sample. In the test, a low temperature bath of −40 ° C. ± 2 ° C. is used, and a covered wire sample and a mandrel having a diameter five times that of the covered wire are placed in a low temperature bath in advance and sufficiently cooled. Thereafter, the covered electric wire is wound around the mandrel three or more times in the low-temperature tank and then taken out from the cooling tank. After returning to room temperature, the wound part of the covered electric wire was visually observed. At this time, a withstand voltage test of 1 kV for 1 minute was conducted for those for which no conductor exposure was observed. And those in which conduction occurred were evaluated as “x” because the low temperature resistance was insufficient.
＜耐摩耗性＞
　ＩＳＯ６７２２に準拠する。７Ｎの荷重、直径０．４５ｍｍの針金、断面積０．１３ｍｍ２の芯線、および、厚さ０．２ｍｍの被覆層を有する被覆電線を用いて、スクレープ摩耗規格で測定を実施し、１００回以上のスクレープに耐えた場合に、耐摩耗性が十分であるとして「○」、１００回未満のスクレープで導通が生じた場合、耐摩耗性が不十分であるとして「×」として、それぞれ評価した。これら評価結果を表２～５に併せて示した。 <Abrasion resistance>
Conforms to ISO6722. Load of 7N, wire diameter 0.45 mm, wire cross-sectional area 0.13 mm 2, and, using a coated electric wire having a coating layer having a thickness of 0.2 mm, measurements were performed in scrape abrasion specification, or 100 times When it was able to withstand this scrape, it was evaluated as “◯” because the wear resistance was sufficient, and when the continuity was generated with less than 100 scrapes, it was evaluated as “x” because the wear resistance was insufficient. These evaluation results are also shown in Tables 2 to 5.
　表２～５より本発明に係る樹脂組成物によれば、安定した被覆電線の製造が可能となり、かつ、得られる被覆電線がＩＳ０　６７２２で規定される自動車用電線の耐バッテリー液性、難燃性、耐低温性、難燃性、及び、耐摩耗性を満足することが判る。 From Tables 2 to 5, according to the resin composition according to the present invention, it is possible to produce a stable covered electric wire, and the obtained covered electric wire is a battery liquid resistance and a flame retardant property of an automobile electric wire specified by IS0 6722. It can be seen that it satisfies the properties of heat resistance, low temperature resistance, flame retardancy, and wear resistance.
　１　　芯線
　２　　被覆層 1 Core wire 2 Coating layer

Claims (2)

  1. 　（Ａ）ポリプロピレン単独重合体４０質量部以上６０質量部以下、（Ｂ）ポリプロピレン系変性樹脂１質量部以上３０質量部以下、（Ｃ）熱可塑性エラストマー１０質量部以上２５質量部以下、及び、（Ｄ）低密度ポリエチレン１質量部以上１５質量部以下からなるベース樹脂１００質量部に対して、表面処理された金属水酸化物が１００質量部以上１８０質量部以下配合されてなることを特徴とする樹脂組成物。 (A) 40 to 60 parts by mass of a polypropylene homopolymer, (B) 1 to 30 parts by mass of a polypropylene-based modified resin, (C) 10 to 25 parts by mass of a thermoplastic elastomer, and ( D) The surface-treated metal hydroxide is blended in an amount of 100 parts by mass to 180 parts by mass with respect to 100 parts by mass of the base resin composed of 1 part by mass to 15 parts by mass of low density polyethylene. Resin composition.
  2. 　請求項１に記載の樹脂組成物によって形成された被覆層を有することを特徴とする被覆電線。 A coated electric wire comprising a coating layer formed of the resin composition according to claim 1.
PCT/JP2014/058484 2013-03-28 2014-03-26 Resin composition and coated electric wire WO2014157314A1 (en)

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CN104610656A (en) * 2015-01-29 2015-05-13 宝鸡石油机械有限责任公司 High and low temperature resin material for plastic coating (impregnating) of steel wire ropes
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JP2002212378A (en) * 2001-01-19 2002-07-31 Sumitomo Wiring Syst Ltd Resin composition, method for producing the same, and electrical wire coated with the same
JP2006225604A (en) * 2005-02-21 2006-08-31 Tmg Kk Flame retardant resin composition
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US20160272801A1 (en) 2016-09-22

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